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Chemistry of Pyrroles [Kõva köide]

(A.E. Favorsky Irkutsk Institute of Chemistry, Russia), (A.E. Favorsky Irkutsk institute of chemistry, Russia), (A.E. Favorsky Irkutsk Institute of Chemistry, Russia), (A.E. Favorsky Irkutsk Institute of Chemistry, Russia)
  • Formaat: Hardback, 398 pages, kõrgus x laius: 234x156 mm, kaal: 680 g, 30 Tables, black and white; 444 Illustrations, black and white
  • Ilmumisaeg: 13-Oct-2014
  • Kirjastus: CRC Press Inc
  • ISBN-10: 1482232421
  • ISBN-13: 9781482232424
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  • Formaat: Hardback, 398 pages, kõrgus x laius: 234x156 mm, kaal: 680 g, 30 Tables, black and white; 444 Illustrations, black and white
  • Ilmumisaeg: 13-Oct-2014
  • Kirjastus: CRC Press Inc
  • ISBN-10: 1482232421
  • ISBN-13: 9781482232424
Teised raamatud teemal:
This book on the chemistry of pyrroles describes a method for the construction of the pyrrole ring from ketones and acetylene in superbase catalytic systems. It details conditions of typical syntheses, limitations of their applicability, and the possibility of vinyl chloride or dichloroethane application instead of acetylene; chemical engineering aspects of the first synthesis of tetrahydroindole and indole from commercially available oxime of cyclohexanone and acetylene; new facets of pyrroles and N-vinyl pyrroles reactivity in the reactions with the participation of the pyrrole ring and N-vinyl groups; and about 1,000 structures of novel pyrrole compounds and their yields and physical-chemical characteristics. Annotation ©2015 Ringgold, Inc., Portland, OR (protoview.com)

During the last 30 years, knowledge of the essential role that pyrrole structures play in the chemistry of living organisms, drug design, and the development of advanced materials has increased. Correspondingly, research on the diverse issues of synthetic, theoretical, and applied chemistry has snowballed. Devoted to the latest achievements of this field,Chemistry of Pyrroles covers the discovery and development of a novel, facile, and highly effective method for the construction of the pyrrole ring from ketones (ketoximes) and acetylene in superbase catalytic systems (Trofimov reaction). It provides cutting-edge details on the preparation of valuable but previously inaccessible pyrrole compounds. It includes approximately 1,000 structures of novel pyrrole compounds, their yields, and physical-chemical characteristics.

The authors analyze conditions of typical syntheses, limitations of their applicability, and possibility of vinyl chloride or dichloroethane application instead of acetylene. They examine chemical engineering aspects of the first synthesis of tetrahydroindole and indole from commercially available oxime of cyclohexanone and acetylene. In addition, the book discusses new facets of pyrroles and N-vinyl pyrroles reactivity in the reactions with the participation of both the pyrrole ring and N-vinyl groups.

The book provides condensed, clear-cut information on novel syntheses of substituted pyrroles as key structural units of living matter (chlorophyll and hemoglobin), pharmaceuticals, and monomers for optoelectronic materials. It includes tables that provide references to original works, forming a guide to a variety of the reactions and synthesized compounds discussed. With coverage of the broad range of pyrrole chemistry and methods for their synthesis, it provides both a theoretical and an experimental basis for drug design.

Preface ix
Introduction xi
Chapter 1 Synthesis of Pyrroles and N-Vinylpyrroles by the Reaction of Ketones (Ketoximes) with Acetylenes 1(128)
1.1 Heterocyclization of Ketoximes with Acetylene
1(76)
1.1.1 Superbase System Alkali Metal Hydroxide-Dimethyl Sulfoxide as the Reaction Catalyst
2(4)
1.1.2 Effects of Base Nature and Concentration
6(3)
1.1.3 Effect of Solvent
9(2)
1.1.4 Effect of Pressure
11(1)
1.1.5 One-Pot Synthesis of Pyrroles from Ketones, Hydroxylamine, and Acetylene
12(4)
1.1.6 Effect of Ketoximes Structure on Yields and Ratio of Pyrroles
16(66)
1.1.6.1 Dialkyl- and Alkylcycloalkylketoximes
16(1)
1.1.6.2 Oximes of Cyclic and Heterocyclic Ketones
16(31)
1.1.6.3 Oximes of Terpenoid Ketones and Their Analogs
47(4)
1.1.6.4 Oximes of Ketosteroids
51(3)
1.1.6.5 Oximes of Alkyl Aryl Ketones
54(4)
1.1.6.6 Oximes of Alkyl Hetaryl Pyrroles
58(6)
1.1.6.7 Functionally Substituted Ketoximes
64(2)
1.1.6.8 Oximes of Diketones: Synthesis of Dipyrroles
66(1)
1.1.6.9 Dioximes of 1,2-Diketones
67(1)
1.1.6.10 Dioximes of 1,3-Diketones
68(3)
1.1.6.11 Dioximes of 1,4-Diketones
71(1)
1.1.6.12 Dioximes Separated by Conjugated Systems
72(5)
1.2 Regiospecificity of the Reaction
77(5)
1.3 Substituted Acetylenes in the Reaction with Ketoximes
82(8)
1.3.1 Methylacetylene
82(2)
1.3.2 Phenylacetylene
84(1)
1.3.3 Acylacetylenes
84(3)
1.3.4 Other Acetylenes
87(3)
1.4 Vinyl Halides and Dihaloethanes as Synthetic Equivalents of Acetylene
90(2)
1.5 Intermediate Stages and Side Reactions
92(21)
1.5.1 Formation of 0-Vinyl Oximes
92(9)
1.5.2 Formation of 4H-2-Hydroxy-2,3-Dihydropyrroles
101(1)
1.5.3 Formation of 3H-Pyrroles
102(1)
1.5.4 Formation of Pyridines
103(4)
1.5.5 Formation of Acetylenic Alcohols
107(1)
1.5.6 Side Products Formed in Trace Amounts
107(6)
1.6 6-Carbolines from 3-Acylindoles and Acetylene
113(2)
1.7 Reaction of Ketoximes with Acetylene in the Presence of Ketones: One-Pot Assembly of 4-Methylene-3-oxa-1- azabicyclo[ 3.1.0]hexanes
115(1)
1.8 Transformations of Aldoximes in the Systems MOH/DMSO and MOH/DMSO/Acetylene
116(3)
1.9 Mechanism of Pyrrole Synthesis from Ketoximes and Acetylene
119(10)
1.9.1 Oximes as Nucleophiles in the Reaction with Acetylenes: Literature Analysis
119(4)
1.9.2 Possible Mechanisms of Pyrrole Synthesis from Ketoximes and Acetylene
123(6)
Chapter 2 Novel Aspects of NH- and N-Vinylpyrroles Reactivity 129(210)
2.1 Reactions with Participation of the Pyrrole Ring
129(169)
2.1.1 Protonation
129(8)
2.1.1.1 Electron Structure of N-Vinylpyrrolium Ions
129(1)
2.1.1.2 Dimerization of Protonated N-Vinylpyrroles
130(1)
2.1.1.3 Peculiarities of N-Vinylpyrroles Protonation with Hydrogen Halides
131(1)
2.1.1.4 Addition of Hydrogen Halides to the Pyrrole Ring
132(1)
2.1.1.5 Protonation of N-Vinylpyrroles with Superacids
132(3)
2.1.1.6 Protonation of Hetarylpyrroles
135(2)
2.1.2 Hydrogenation and Dehydrogenation
137(5)
2.1.2.1 Hydrogenation
137(2)
2.1.2.2 Selective Dehydrogenation of 4,5,6,7-Tetrahydroindole
139(1)
2.1.2.3 Dehydrogenation of 4,5-dihydrobenz[ g]indole
139(3)
2.1.3 Reactions with Electrophilic Alkenes
142(12)
2.1.3.1 Nucleophilic Addition to Vinyl Sulfones
142(3)
2.1.3.2 Reactions with Tetracyanoethylene
145(9)
2.1.4 Reactions with Acetylene
154(14)
2.1.4.1 N-Vinylation
154(3)
2.1.4.2 Reactions with Electrophilic Acetylenes
157(10)
2.1.4.3 Reactions with 1-Alkylthio-2- chloroacetylenes
167(1)
2.1.5 Cross-Coupling of Pyrroles with Haloacetylenes
168(25)
2.1.5.1 Ethynylation of Pyrroles
168(14)
2.1.5.2 Reaction of 2-Ethynylpyrroles with 2,3-Dichloro-5,6-dicyano-1,4- benzoquinone
182(8)
2.1.5.3 Hydroamination of 2-Ethynylpyrroles
190(3)
2.1.6 Reactions with Carbon Disulfide
193(49)
2.1.6.1 Synthesis of Pyrrolecarbodithioates
193(9)
2.1.6.2 Addition of Pyrrolecarbodithioate Anions to the Multiple Bond
202(3)
2.1.6.3 Reactions of S-Alkylpyrrolecarbodithioates
205(1)
2.1.6.4 Synthesis of Pyrrolothiazolidines
206(1)
2.1.6.5 Synthesis of Pyrrolizin-3-One
206(8)
2.1.6.6 Reactions of Functionally Substituted C-Vinylpyrroles with Hydroxide Anion: Synthesis of Stable Enols
214(10)
2.1.6.7 Reactions of Functionalized 2-Vinylpyrroles with Amines
224(3)
2.1.6.8 Synthesis of 5-Amino-3-(pyrrol-2-yl) pyrazoles
227(9)
2.1.6.9 Synthesis of 5(3)-Amino-3(5)-(pyrrol- 2-yl)isoxazoles
236(6)
2.1.7 Alkylation of Pyrroles with Functional Organic Halides
242(6)
2.1.7.1 Alkylation of Pyrroles with Allyl Halides
242(1)
2.1.7.2 Alkylation of Pyrroles with Propargyl Halides
243(1)
2.1.7.3 Allenylation of Pyrroles with 2,3-Dichloro-1-propene
243(3)
2.1.7.4 Allenylation of Pyrroles with 1,2,3-Trichloropropane
246(1)
2.1.7.5 Ethynylation of Pyrroles with 1,2-Dichloroethene
247(1)
2.1.7.6 Ethynylation of Pyrroles with Trichloroethene
247(1)
2.1.7.7 Epoxymethylation of Pyrroles with Epichlorohydrin
247(1)
2.1.8 Formylation of Pyrroles and Reactions of N-Vinylpyrrole-2-carbaldehydes
248(24)
2.1.8.1 Synthesis of N-Vinylpyrrole-2- carbaldehydes
248(2)
2.1.8.2 Reactions of Pyrrole-2-carbaldehydes with Aromatic Di- and Tetraamines
250(14)
2.1.8.3 Reactions of Pyrrole-2-carbaldehydes with Hydroxylamine, Semicarbazide, Thiosemicarbazide, and Aminoguanidine
264(2)
2.1.8.4 Reactions of N-Vinylpyrrole-2- carbaldehydes with L-Lysine
266(2)
2.1.8.5 Three-Component Reaction of N-Vinylpyrrole-2-carbaldehydes with N-Methylimidazole and Cyanophenylacetylene
268(1)
2.1.8.6 Thiylation of N-Vinylpyrrole-2- carbaldehydes
269(2)
2.1.8.7 N-Vinylpyrrole-2-carbaldehydes as Precursors of N-Vinylpyrrole-2-carbonitriles
271(1)
2.1.9 Trifluoroacetylation
272(11)
2.1.10 Azo Coupling
283(9)
2.1.11 Assembly of 4,4-Difluoro-4-bora-3a,4a-diaza-s-indacenes
292(6)
2.1.11.1 Via Meso-Aryldipyrromethenes
292(5)
2.1.11.2 Via Meso-CF3-Dipyrromethenes
297(1)
2.2 Reactions with Participation of the Vinyl Group
298(39)
2.2.1 Hydrolysis
298(3)
2.2.2 Electrophilic Addition of Alcohols and Phenols
301(18)
2.2.3 Addition of Thiols
319(2)
2.2.4 Hydrosilylation
321(2)
2.2.5 Addition of Secondary Phosphines
323(1)
2.2.6 Reactions with Halophosphines
324(1)
2.2.7 Reactions with Phosphorus Pentachloride
325(3)
2.2.8 Catalytic Arylation of the Vinyl Group (Heck Reaction)
328(1)
2.2.9 Metalation of N-Vinylpyrroles and Their Analogs
329(6)
2.2.9.1 Metalation of N-Vinylpyrrole
329(3)
2.2.9.2 Metalation of N-Allenylpyrrole
332(3)
2.2.9.3 Metalation of N-Ethynylpyrrole
335(1)
2.2.10 Devinylation
335(2)
2.3 Conclusions
337(2)
References 339(36)
Index 375
Boris A. Trofimov, Al'bina I. Mikhaleva, Elena Yu Schmidt, Lyubov N. Sobenina